Characteristics and sources of peroxyacetyl nitrate (PAN) in the rural North China Plain: Results from 1-year continuous observations.

Peroxyacetyl nitrate (PAN) is an important photochemical pollutant in the troposphere, whereas long-term measurements are scarce in rural areas in North China Plain (NCP), resulting in unclear seasonal variations and sources of PAN in rural NCP. In this study, we conducted a 1-year observation of PAN during 2021-2022 at the rural NCP site. The average concentrations of PAN were 1.10, 0.75, 0.65, and 0.88 ppbv in spring, summer, autumn, and winter, respectively, with a 1-year average of 0.81 ± 0.60 ppbv. Calculations indicate that the loss of PAN through thermal decomposition in summer accounts for 43.2% of the total formed PAN, which is an important reason for the low concentration of PAN in summer. We speculate that since the correlation between PAN and O3 in winter is significantly lower than that in other seasons, the observed regional transport of PAN cannot be ignored in winter. Through budget analysis, regional transport accounted for 12.8% and 55.9% of the observed PAN on the spring and winter pollution days, respectively, which showed that regional transport played key roles during the photochemical pollution of the rural NCP in winter. The potential source contribution function revealed that the transported PAN mainly comes from southern Hebei in spring. In winter, the transported PAN was mainly from Langfang, Hengshui, and southern Beijing. Our findings may aid in understanding PAN variations in different seasons in rural areas and highlight the impact of regional transport on the PAN budget.

A comprehensive observation on the pollution characteristics of peroxyacetyl nitrate (PAN) in Beijing, China.

Peroxyacetyl nitrate (PAN) is a typical secondary photochemical product in the atmospheric environment with significant adverse effects on human health and plant growth. In this study, PAN and other pollutants, as well as meteorological conditions were observed intensively from August to September in 2022 at a typical urban sampling site in Beijing, China. The mean and maximum PAN concentrations during the observation period were 1.00 ± 0.97 ppb and 4.84 ppb, respectively. Severe photochemical pollution occurred during the observation period, with the mean PAN concentration about 3.1 times higher than that during the clean period. There was a good positive correlation between O3 and PAN, and their correlation was higher during the O3 exposure period than that during the clean period. The simulated results by box-model coupled with the Master Chemical Mechanism (MCM v3.3.1) showed that the O3-related reactions were the largest sources of OH radicals during O3 exposure period, which was conducive to the co-contamination of PAN and O3. Acetaldehyde (CH3CHO) and methylglyoxal (MGLY) were the largest OVOCs precursors of peroxyacetyl radicals (PA), with the contributions to the total PA generated by OVOCs about 67 % - 83 % and 17 % - 30 %, respectively. The reduction of emissions from liquefied petroleum gas (LPG) and solvent usage has the highest reduction effect on PAN and O3, followed by the control of gasoline vehicle exhaust emissions. This study deepens the understanding of the PAN photochemistry in urban areas with high O3 background conditions and the impact of anthropogenic activities on the photochemical pollution. Meanwhile, the findings of this study highlight the necessity of strengthening anthropogenic emissions control to effectively reduce the co-contamination of PAN and O3 in Beijing in the future.

The Lack of HONO Measurement May Affect the Accurate Diagnosis of Ozone Production Sensitivity.

Recently, deteriorating ozone (O3) pollution in China brought the precise diagnosis of O3 sensitive chemistry to the forefront. As a dominant precursor of OH radicals, atmospheric nitrous acid (HONO) plays an important role in O3 production. However, its measurement unavailability in many regions especially for second- and third-tier cities may lead to the misjudgment of the O3 sensitivity regime derived from observation-based models. Here, we systematically assess the potential impact of HONO on diagnosing the sensitivity of O3 production using a 0-dimension box model based on a comprehensive summer urban field campaign. The results indicated that the default mode (only the NO + OH reaction is included) in the model could underestimate ∼87% of observed HONO levels, leading to an obvious decrease (∼19%) of net O3 production in the morning, which was in line with the previous studies. The unconstrained HONO in the model was found to significantly push O3 production toward the VOC-sensitive regime. Additionally, it is unrealistic to change NO x but constrain HONO in the model due to the dependence of HONO formation on NO x . Assuming that HONO varied proportionally with NO x , a stronger NO x -sensitive condition could be achieved. Therefore, effective reduction of NO x should be given more attention together with VOC emission control for O3 mitigation.

Aging of pollution air parcels acts as the dominant source for nocturnal HONO.

Atmospheric HONO acts as a major source for OH radicals in polluted areas, playing an important role in formation of secondary pollutants. However, the atmospheric HONO sources remain unclear. Here we propose that the heterogeneous reaction of NO2 on aerosols during aging processes acts as the dominant source for nocturnal HONO. Based on the nocturnal variations of HONO and related species in Tai'an city of China, we firstly developed new method to estimate the localized HONO dry deposition velocity (v(HONO)). The estimated v(HONO) of 0-0.077 m/s was in a good agreement with the reported ranges. Additionally, we set up a parametrization to reflect the HONO formation from the aged air parcels based on the variation of HONO/NO2 ratio. The detailed variation of nocturnal HONO could be well reproduced by a complete budget calculation coupled with above parameterizations, with the difference between the observed and calculated HONO levels being <5 %. The results also revealed the average contribution of HONO formation from aged air parcels to atmospheric HONO could achieve to be ~63 % in average.

A novel photochemical conversion technique for reliable calibration of peroxyacetyl nitrate (PAN) analyzers.

Photochemical synthesis of peroxyacetyl nitrate (PAN) through irradiating air mixtures of NO and acetone is prevailingly adopted for calibrating PAN analyzers, but few users of PAN analyzers provide evidence to certify the calibration reliability. Here we report a nonnegligible variation (up to ~50 %) of PAN synthesized in the calibration unit of a commercial PAN analyzer, whereas PAN synthesized in the two custom-made reactors could achieve stable values with variations of <2.5 %. Compared with a straight quartz tube flow reactor (SQTFR), PAN synthesized by a coiled quartz tube flow reactor (CQTFR) could achieve more stable (relative standard deviation: <0.66 % versus 2.49 %) and larger (PANCQTFR/PANSQTFR: 1.04-1.10) values. The residence time and reaction temperature of photochemical mixtures in CQTFR were found to be the key factors affecting PAN synthesis, with their optimal values of 30-60 s and 30-35 °C for achieving the highest PAN levels. The photochemical conversion efficiencies of NO to PAN in CQTFR under the optimal conditions were successfully measured to be 98.5 ± 0.5 % based on the alkaline-absorption method. Therefore, CQTFR is suggested to be adopted for calibrating PAN analyzers to reduce calibration uncertainties.

Ambient volatile organic compounds in urban and industrial regions in Beijing: Characteristics, source apportionment, secondary transformation and health risk assessment.

Field measurements of volatile organic compounds (VOCs) were conducted simultaneously at an urban site and one industrial park site in Beijing in summer. The VOCs concentrations were 94.3 ± 157.8 ppbv and 20.7 ± 8.9 ppbv for industrial and urban sites, respectively. Alkanes and aromatics were the major contributors to VOCs in industrial site, while oxygenated volatile organic compounds (OVOCs) contributed most in urban site. The most abundant VOC species were n-pentane and formaldehyde for industrial site and urban site, respectively. The calculated ozone formation potential (OFP) and OH loss rates (LOH) were 621.1 ± 1491.9 ppbv (industrial site), 102.9 ± 37.3 ppbv (urban site), 22.0 ± 39.0 s-1 (industrial site) and 5.3 ± 2.2 s-1 (urban site), respectively. Based on the positive matrix factorization (PMF) model, solvent utilization I (34.1 %), solvent utilization II (27.9 %), mixture combustion source (19.3 %), OVOCs related source (9.6 %) and biogenic source (9.1 %) were identified in the industrial site, while OVOCs related source (27.8 %), vehicle exhaust (22.1 %), solvent utilization (19.3 %), coal combustion (16.0 %) and biogenic source (14.8 %) were identified in the urban site. The results of O3-VOCs-NOx sensitivity indicated that O3 formation were respectively under the VOC-limited and NOx-limited conditions in Beijing urban and industrial regions. Additionally, aromatics accounted remarkable SOA formation ability both in the two sites, and SOA potentials of xylene, toluene and ethylbenzene as the indicator species for the solvent utilization in industrial site were remarkable higher than those obtained in urban regions. The hazard index values in the industrial and urban sites were 1.72 and 3.39, respectively, suggesting a high non-carcinogenic risks to the exposed population. Formaldehyde had the highest carcinogenic risks in the two sites, and the cumulative carcinogenic risks in the industrial site and urban site were 1.95 × 10-5 and 1.21 × 10-5, respectively.

Strong impacts of biomass burning, nitrogen fertilization, and fine particles on gas-phase hydrogen peroxide (H2O2).

Gas-phase hydrogen peroxide (H2O2) plays an important role in atmospheric chemistry as an indicator of the atmospheric oxidizing capacity. It is also a vital oxidant of sulfur dioxide (SO2) in the aqueous phase, resulting in the formation of acid precipitation and sulfate aerosol. However, sources of H2O2 are not fully understood especially in polluted areas affected by human activities. In this study, we reported some high H2O2 cases observed during one summer and two winter campaigns conducted at a polluted rural site in the North China Plain. Our results showed that agricultural fires led to high H2O2 concentrations up to 9 ppb, indicating biomass burning events contributed substantially to primary H2O2 emission. In addition, elevated H2O2 and O3 concentrations were measured after fertilization as a consequence of the enhanced atmospheric oxidizing capacity by soil HONO emission. Furthermore, H2O2 exhibited unexpectedly high concentration under high NOx conditions in winter, which are closely related to multiphase reactions in particles involving organic chromophores. Our findings suggest that these special factors (biomass burning, fertilization, and ambient particles), which are not well considered in current models, are significant contributors to H2O2 production, thereby affecting the regional atmospheric oxidizing capacity and the global sulfate aerosol formation.

Rural vehicle emission as an important driver for the variations of summertime tropospheric ozone in the Beijing-Tianjin-Hebei region during 2014-2019.

Tropospheric ozone (O3) pollution is increasing in the Beijing-Tianjin-Hebei (BTH) region despite a significant decline in atmospheric fine aerosol particles (PM2.5) in recent years. However, the intrinsic reason for the elevation of the regional O3 is still unclear. In this study, we analyzed the spatio-temporal variations of tropospheric O3 and relevant pollutants (PM2.5, NO2, and CO) in the BTH region based on monitoring data from the China Ministry of Ecology and Environment during the period of 2014-2019. The results showed that summertime O3 concentrations were constant in Beijing (BJ, 0.06 µg/(m3•year)) but increased significantly in Tianjin (TJ, 9.09 µg/(m3•year)) and Hebei (HB, 6.06 µg/(m3•year)). Distinct O3 trends between Beijing and other cities in BTH could not be attributed to the significant decrease in PM2.5 (from -5.08 to -6.32 µg/(m3•year)) and CO (from -0.053 to -0.090 mg/(m3•year)) because their decreasing rates were approximately the same in all the cities. The relatively stable O3 concentrations during the investigating period in BJ may be attributed to a faster decreasing rate of NO2 (BJ: -2.55 µg/(m3•year); TJ: -1.16 µg/(m3•year); HB: -1.34 µg/(m3•year)), indicating that the continued reduction of NOx will be an effective mitigation strategy for reducing regional O3 pollution. Significant positive correlations were found between daily maximum 8 hr average (MDA8) O3 concentrations and vehicle population and highway freight transportation in HB. Therefore, we speculate that the increase in rural NOx emissions due to the increase in vehicle emissions in the vast rural areas around HB greatly accelerates regional O3 formation, accounting for the significant increasing trends of O3 in HB.

Evaluation of offline sampling for atmospheric C3-C11 non-methane hydrocarbons.

The concentration variation of C3-C11 non-methane hydrocarbons (NMHCs) collected in several types of commercial flexible bags and adsorption tubes was systematically investigated using a gas chromatography-flame ionization detector (GC-FID) system. The percentage loss of each NMHC in the polyvinyl fluoride (PVF) bags was less than 5% during a 7-hr storage period; significant NMHCs loss was detected in aluminum foil composite film and fluorinated ethylene propylene bags. The thermal desorption efficiency of NMHCs for adsorption tubes filled Carbopack B and Carboxen1000 sorbents was greater than 95% at 300℃, and the loss of NMHCs in the adsorption tubes during 20-days storage at 4℃ was less than 8%. The thermal desorption efficiency for C11 NMHCs in the adsorption tube filled with Carbograph 1 and Carbosieve SⅢ absorbents was less than 40% at 300℃, and pyrolysis of the absorbents at 330℃ interfered significantly with the measurements of some alkenes. The loss of alkenes was significant when NMHCs were sampled by cryo-enrichment at -90℃ in the presence of O3 for the online NMHC measurements, and negligible for enrichment using adsorption tubes at 25℃. Although O3 scrubbers have been widely used to eliminate the influence of O3 on NMHC measurements, the loss of NMHCs with carbon numbers greater than 8 was more than 10%. Therefore, PVF bags and adsorption tubes filled Carbopack B and Carboxen1000 sorbents were recommended for the sampling of atmospheric NMHCs.

Abiotic degradation of field wheat straw as a notable source of atmospheric carbonyls in the North China Plain.

Carbonyl compounds (carbonyls) play a crucial role in atmospheric chemistry, but their atmospheric sources are not fully identified. Here we show unexpectedly high carbonyl emissions from extensive field returning wheat straw over the North China Plain (NCP). The emission rates of carbonyls exhibit distinct diurnal variations with the noontime peak value of total carbonyls greater than 135 µg∙kg-1 (dry straw weight) ∙h-1. The carbonyl emission is mainly attributed to biomass abiotic degradation processes that are affected by air temperature and sunlight intensity. Given that the photolysis of carbonyls is the major primary source of ROx radicals in the troposphere, carbonyl emissions would lead to increasing atmospheric oxidants. The mean daytime O3 concentration over the NCP increases by 12.3% when coupling carbonyl emissions from wheat straw with the current emission inventory through the model simulation. It might be one of the important reasons for the occurrence of the most serious O3 pollution in June when winter wheat is intensively harvested in the region. Further studies are warranted to explore the influence of field returning wheat straw on regional air quality.

Photochemical Aging of Atmospheric Fine Particles as a Potential Source for Gas-Phase Hydrogen Peroxide.

Atmospheric hydrogen peroxide (H2O2), as an important oxidant, plays a key role in atmospheric sulfate formation, affecting the global radiation budget and causing acid rain deposition. The disproportionation reactions of hydroperoxyl radicals (HO2) in both gas and aqueous phases have long been considered as dominant sources for atmospheric H2O2. However, these known sources cannot explain the significant formation of H2O2 in polluted areas under the conditions of high NO levels and low ambient relative humidity (RH). Here, we show that under relatively dry conditions during daytime, atmospheric fine particles directly produce abundant gas-phase H2O2. The formation of H2O2 is verified to be by a reaction between the particle surface -OH group and HO2 radicals formed by photooxidation of chromophoric dissolved organic matters (CDOMs), which is slightly influenced by the presence of high NO levels but remarkably accelerated by water vapor and O2. In contrast to aqueous-phase chemistry, transition metal ions (TMIs) are found to significantly suppress H2O2 formation from the atmospheric fine particles. The H2O2 formed from relatively dry particles can be directly involved in in situ SO2 oxidation, leading to sulfate formation. As CDOMs are ubiquitous in atmospheric fine particles, their daytime photochemistry is expected to play important roles in formation of H2O2 and sulfate worldwide.

A comparison investigation of atmospheric NMHCs at two sampling sites of Beijing city and a rural area during summertime.

Atmospheric non-methane hydrocarbons (NMHCs) were measured synchronously at an urban site of Beijing city (BJ) and a rural site of Dongbaituo (DBT) in Hebei province from 1 July to 15 August 2016. The average concentration of the total NMHCs (TNMHCs) at DBT site were about a factor of 1.3 higher than that at BJ site. Ethane, ethylene, propane, acetylene, butane, isobutane, toluene and isopentane were the common species in the top ten NMHCs at the two sampling sites, and the contributions of the top ten NMHCs to TNMHCs at BJ and DBT sites were 65.6% and 75.1%, respectively. The diurnal variations of TNMHCs at BJ site exhibited one peak during the morning rush hours, whereas two peaks occurred at DBT site during the period from 3:00 to 8:00 (UTC/GMTC8). Based on the correlation coefficients of typical NMHCs pairs and the positive matrix factorization (PMF) results, the gasoline exhaust was found to be the dominant source (38.8%) for atmospheric NMHCs in Beijing, while coal combustion made the largest contribution (32.3%) at the rural site. Atmospheric ozone production over the BJ site was found to be NMHCs-sensitive, while it was in the transition regime at DBT site. Additionally, the largest contributions of atmospheric NMHCs groups to the ozone formation potential at BJ and DBT sites were alkenes and aromatics, with the proportions of 35.8% and 38.6%, respectively.

Pollution levels, composition characteristics and sources of atmospheric PM2.5 in a rural area of the North China Plain during winter.

The pollution levels, composition characteristics and sources of atmospheric PM2.5 were investigated based on field measurement at a rural site in the North China Plain (NCP) from pre-heating period to heating period in winter of 2017. The hourly average concentrations of PM2.5 frequently exceeded 150 µg/m3 and even achieved 400 µg/m3, indicating that the PM2.5 pollution was still very serious despite the implementation of stricter control measures in the rural area. Compared with the pre-heating period, the mean concentrations of organic carbon (OC), element carbon (EC) and chlorine ion (Cl-) during the heating period increased by 20.8%, 36.6% and 38.8%, accompanying with increments of their proportions in PM2.5 from 37.5%, 9.8% and 5.5% to 42.9%, 12.7% and 7.2%, respectively. The significant increase of both their concentrations and proportions during the heating period was mainly ascribed to the residential coal combustion. The proportions of sulfate, nitrate and ammonium respectively increased from 9.9%, 10.9% and 9.0% in nighttime to 13.8%, 16.2% and 11.1% in daytime, implying that the daytime photochemical reactions made remarkable contributions to the secondary inorganic aerosols. The simulation results from WRF-Chem revealed that the emission of residential coal combustion in the rural area was underestimated by the current emission inventory. Six sources identified by positive matrix factorization (PMF) based on the measurement were residential coal combustion, secondary formation of inorganic aerosols, biomass burning, vehicle emission and raising dust, contributing to atmospheric PM2.5 of 40.5%, 21.2%, 16.4%, 10.8%, 8.6% and 2.5%, respectively.

Characteristics and influence factors of NO2 exchange flux between the atmosphere and P. nigra.

Nitrogen dioxide (NO2) is an important substance in atmospheric photochemical processes and can also be absorbed by plants. NO2 fluxes between the atmosphere and P. nigra seedlings were investigated by a double dynamic chambers method in Beijing from June 15 to September 3, 2017. The range of NO2 exchange fluxes between P. nigra seedlings and the atmosphere was from -14.6 to 0.8 nmol/(m2·sec) (the positive data represent NO2 emission from trees, while the negative values indicate absorption). Under ambient concentrations, the mean NO2 flux during the fast-growing stage (Jun. 15-Aug. 4) was -3.0 nmol/(m2·sec), greater than the flux of -1.5 nmol/(m2·sec) during the later growth stage (Aug. 8-Sept. 3). The daily exchange fluxes of NO2 obviously fluctuated. The fluxes were largest in the morning and decreased gradually over time. Additionally, the NO2 fluxes were larger under high light intensities than under low light intensities during the whole growth period. The effects of temperature on NO2 fluxes were different under two growth periods. The NO2 exchange fluxes were larger in a range of temperatures close to 44°C in the fast-growing stage, whereas there were no evident differences in NO2 exchange fluxes under widely differing temperatures in the later growth stage. Under polluted conditions, the uptake ability of NO2 was weakened. Additionally, the compensation point of NO2 was 5.6 ppb in the fast-growing stage, whereas it was 1.4 ppb in the later growth stage. The deposition velocities of NO2 were between 0.3 and 2.4 mm/sec.

Activity maintenance of the excised branches and a case study of NO2 exchange between the atmosphere and P. nigra branches.

The efficient maintenance of the activity of excised branches is the powerful guarantee to accurately determine gas exchange flux between the detached branches of tall trees and the atmosphere. In this study, the net photosynthetic rate (NPR) of the excised branches and branches in situ were measured simultaneously by using two photosynthetic instruments to characterize the activity of the excised branches of Phyllostachys nigra. The ratio of normalized NPR of excised branches to NPR in situ was used to assess the photosynthetic activity of detached branches. Based on photosynthetic activity, an optimal hydroponics protocol for maintaining activity of excised P. nigra branches was presented: 1/8 times the concentration of Gamborg B5 vitamin mixture with pH = 6. Under the best cultivation protocol, photosynthetic activity of excised P. nigra branches could be maintained more than 90% within 6 hr in the light intensity range of 200-2000 µmol/(m2·sec) and temperature range of 13.4-28.7°C. The nitrogen dioxide (NO2) flux differences between in situ and in vitro branches and the atmosphere were compared using double dynamic chambers. Based on the maintenance method of excised branches, the NO2 exchange flux between the excised P. nigra branches and the atmosphere (from -1.01 to -2.72 nmol/(m2·sec) was basically consistent with between the branches in situ and the atmosphere (from -1.12 to -3.16 nmol/(m2 sec)) within 6 hr. Therefore, this study provided a feasible protocol for in vitro measurement of gas exchange between tall trees and the atmosphere for a period of time.

The levels, sources and reactivity of volatile organic compounds in a typical urban area of Northeast China.

Air concentrations of volatile organic compounds (VOCs) were continually measured at a monitoring site in Shenyang from 20 August to 16 September 2017. The average concentrations of alkanes, alkenes, aromatics and carbonyls were 28.54, 6.30, 5.59 and 9.78 ppbv, respectively. Seven sources were identified by the Positive Matrix Factorization model based on the measurement data of VOCs and CO. Vehicle exhaust contributed the most (36.15%) to the total propene-equivalent concentration of the measured VOCs, followed by combustion emission (16.92%), vegetation emission and secondary formation (14.33%), solvent usage (10.59%), petrochemical industry emission (9.89%), petrol evaporation (6.28%), and liquefied petroleum gas (LPG) usage (5.84%). Vehicle exhaust, solvent usage and combustion emission were found to be the top three VOC sources for O3 formation potential, accounting for 34.52%, 16.55% and 11.94%, respectively. The diurnal variation of the total VOCs from each source could be well explained by their emission characteristics, e.g., the two peaks of VOC concentrations from LPG usage were in line with the cooking times for breakfast and lunch. Wind rose plots of the VOCs from each source could reveal the possible distribution of the sources around the monitoring site. The O3 pollution episodes during the measurement period were found to be coincident with the elevation of VOCs, which was mainly due to the air parcel from the southeast direction where petrochemical industry emission was found to be dominant, suggesting that the petrochemical industry emission from the southeast was probably a significant cause of O3 pollution in Shenyang.

Photochemical production of carbonyl sulfide, carbon disulfide and dimethyl sulfide in a lake water.

Photochemical production of carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl sulfide (DMS) was intensively studied in the water from the Aohai Lake of Beijing city. The lake water was found to be highly supersaturated with COS, CS2 and DMS, with their initial concentrations of 0.91±0.073nmol/L, 0.55±0.071nmol/L and 0.37±0.062nmol/L, respectively. The evident photochemical production of COS and CS2 in the lake water under irradiation of 365nm and 302nm indicated that photochemical production of them might be the reason for their supersaturation. The similar dependence of wavelength and oxygen for photochemical production of COS, CS2 and DMS implied that they might be from the same precursors. The water cage effect was found to favor COS production but inhibit CS2 and DMS formation, indicating that COS photochemical production was mainly from direct degradation of the precursors and the formation of CS2 and DMS needed intermediates via combination of carbon-centered radicals and sulfur-centered radicals. The above assumptions were further confirmed by simulation experiments with addition of carbonyls and amino acids (cysteine and methionine), and the photochemical formation mechanisms for COS, CS2 and DMS in water were derived from the investigations.

Emission of volatile organic compounds from domestic coal stove with the actual alternation of flaming and smoldering combustion processes.

Volatile organic compounds (VOCs) emissions from the chimney of a prevailing domestic stove fuelled with raw bituminous coal were measured under flaming and smoldering combustion processes in a farmer's house. The results indicated that the concentrations of VOCs quickly increased after the coal loading and achieved their peak values in a few minutes. The peak concentrations of the VOCs under the smoldering combustion process were significantly higher than those under the flaming combustion process. Alkanes accounted for the largest proportion (43.05%) under the smoldering combustion, followed by aromatics (28.86%), alkenes (21.91%), carbonyls (5.81%) and acetylene (0.37%). The emission factors of the total VOCs under the smoldering combustion processes (5402.9 ± 2031.8 mg kg-1) were nearly one order of magnitude greater than those under the flaming combustion processes (559.2 ± 385.9 mg kg-1). Based on the VOCs emission factors obtained in this study and the regional domestic coal consumption, the total VOCs emissions from domestic coal stoves was roughly estimated to be 1.25 × 108 kg a-1 in the Beijing-Tianjin-Hebei region.

Development of gas chromatography-flame ionization detection system with a single column and liquid nitrogen-free for measuring atmospheric C2-C12 hydrocarbons.

A liquid nitrogen-free GC-FID system equipped with a single column has been developed for measuring atmospheric C2-C12 hydrocarbons. The system is consisted of a cooling unit, a sampling unit and a separation unit. The cooling unit is used to meet the temperature needs of the sampling unit and the separation unit. The sampling unit includes a dehydration tube and an enrichment tube. No breakthrough of the hydrocarbons was detected when the temperature of the enrichment tube was kept at -90 °C and sampling volume was 400 mL. The separation unit is a small round oven attached on the cooling column. A single capillary column (OV-1, 30 m × 0.32 mm I.D.) was used to separate the hydrocarbons. An optimal program temperature (-60 ∼ 170 °C) of the oven was achieved to efficiently separate C2-C12 hydrocarbons. There were good linear correlations (R(2)=0.993-0.999) between the signals of the hydrocarbons and the enrichment amount of hydrocarbons, and the relative standard deviation (RSD) was less than 5%, and the method detection limits (MDLs) for the hydrocarbons were in the range of 0.02-0.10 ppbv for sampling volume of 400 mL. Field measurements were also conducted and more than 50 hydrocarbons from C2 to C12 were detected in Beijing city.

Serious BTEX pollution in rural area of the North China Plain during winter season.

Atmospheric BTEX compounds (benzene, toluene, ethylbenzene and xylenes) in a rural site of the North China Plain (NCP) were preliminarily investigated in winter, and the outdoor concentrations (25.8-236.0 µg/m3) were found to be much higher than those reported in urban regions. The pollution of BTEX inside a farmer's house was even more serious, with combined concentrations of 254.5-1552.9 µg/m3. Based on the ratio of benzene to toluene (1.17±0.34) measured, the serious BTEX pollution in the rural site was mainly ascribed to domestic coal combustion for heating during the winter season. With the enhancement of farmers' incomes in recent years, coal consumption by farmers in the NCP is rapidly increasing to keep their houses warm, and hence the serious air pollution in rural areas of the NCP during winter, including BTEX, should be paid great attention.